Alkali cellulose compositions



Patented July 1, 1952 Erica T E I ALKALI CELLULOSE COMPOSITIONS Albert B. Savage and Richard W. Swinehart, Midland, Mich., adsignors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware No Drawing. Application June 4, 1947, Serial No. 752,571

' 1 Claim. 1

This invention relates to the manufacture of water-soluble methyl cellulose, and is concerned particularly with an improvement in the economy and quality of such manufacture. It relates as well to a new high viscosity methyl cellulose of high solubility in water.

During the past 30 years, methyl cellulose has been developed from a laboratory curiosity to a technically important commercial product. The fact that it may be soluble in cold water, or in dilute alkali (with or without a freezing step), depending on the degree of substitution, is well known. While the alkali-soluble materials, of a relatively low degree of etherification, are important products, the type of methyl cellulose which can be dissolved in water is even more important, and is the one here concerned.

Many suggestions have been made to improve the older processes for making water-soluble methyl cellulose. These have dealt not only with the choice of methylating, i. e. etherifying agent, and the temperature and duration of the etheri fication reaction, but also with the character oi the alkali cellulose to be etherified and' the methods whereby the chosen type of alkali cellulose may be made. Many of the processes have differed chiefly in the choice of particular concentrations of alkali and ratios of alkali and of water to the cellulose. Two contributions to this art, in recent years, have been disclosed by Lilienfeld, U. S. 2,103,952 and by Maasberg, U. S. 2,160,782.

The Lilienfeld Patent 2,103,952 discloses the reaction of a methyl halide with an alkali cellulose having an alkali to cellulose ratio of from 0.3 parts to 0.8 parts of alkali per part of cellulose, and a water to cellulose ratio of at least 0.5 parts of water per part of cellulose, the quantity of water being in every case greater than that of alkali, but smaller than 3 times the weight of alkali calculated as sodium hydroxide. The alkali cellulose, then, contains alkali and water in ratios equivalent to sodium hydroxide solutions of from 49 to 26 per cent.

The Maasberg Patent 2,160,782, discloses the reaction of methyl halides or sulfate with an al kali cellulose containing from 0.9 to 1.2 parts of sodium hydroxide and from 0.9 to 1.5 parts of water, per part of cellulose. This alkali cellulose contains alkali and water in ratios equivalent to sodium hydroxide solutions of from about 38 to about 5'7 per cent. The reaction, when carried out as described, yields a methyl cellulose with a methoxyl content of from 25 to 33 per cent, 1. e. from 1.5 to 2 methoxyl groups per 06 unit in the cellulose.

It is well known that sodium hydroxide solutions of high concentration penetrate sheets of cellulose fibers less readily than do more dilute solutions. On the other hand, it is generally believed that the larger amounts of water present in an alkali cellulose made from dilute sodium hydroxide are unduly destructive of the etherifying agent, leading to the formation of unnecessarily large amounts of methyl alcohol and methyl ether as by-products. The more concentrated the alkali solution, however, the greater is the degradation of the cellulose, and the lower is the viscosity of the methyl cellulose obtained by etherification. These and other problems associated with methyl cellulose manufacture give rise to the following objects of the present invention.

It is among the objects of this invention to provide a method for the production of a uniformly substituted, water-soluble methyl cellucellulose. The crux of the invention resides in lose with an improved efficiency in the etherification-reaction. Another object is to provide an economical method for the production of a uniform, water-soluble methyl cellulose of high viscosity. A further object is to provide a method whereby a sheet of cellulose fibers may be uniformly impregnated with sodium hydroxide solution, with minimum degradation of the cellulose, to provide an alkali cellulose which yields a water-soluble methyl cellulose upon etherification with a methyl halide or sulfate. A particular object is to provide a method for producing from wood pulp a methyl cellulose having at least as high a viscosity as has been obtained heretofore from cotton fibers, and one which produces from cotton pulp a methyl cellulose of heretofore unobtainably high viscosity. The general object is the provision of a particularly advantageous and economical process for the production of water-soluble methyl cellulose of high quality. Yet another object is the provision of an improved high viscosity methyl cellulose.

The foregoing and related objects have been fulfilled by the present invention, which consists essentially in reacting an alkali cellulose of a particular. narrow range of compositions, with a methyl halide or sulfate in amount at least equivalent to the amount of sodiumhydroxide present, until the sodium hydroxide is almost fully neutralized, and recovering the methyl the particular composition of the alkali cellulose employed in the otherwise customary type of etherification reaction. The use of that alkali cellulose makes possible the use of smaller charges of etherifying agents, as will be shown hereinafter, and leads to a general economy in reagents and the production of a much improved product of high viscosity.

According to the invention, the alkali cellulose employed is one which contains at least 0.9 and not over 1.2 parts by weight of sodium hydroxide, per part of cellulose, and .atleast 1.6 and not much over 2.25 parts of water, per-part of cellulose, and in which the .ratioof .alkali'to water represents a sodium hydroxide solution of from 32 to 38 per cent concentration. Such an Example 1.-Methyl cellulose from cotton linters A sheet of 600 second cotton linters was dipped in asodium hydroxide solution of 35 per cent concentration and was pressed to provide the ind'ioatedratios of alkali and of water to cellulose.

alkali cellulose is prepared, according to the in- 5 Other conditions of treatment are set forth in the vention, by passing a felted sheet of cellulose following Table I. The alkali cellulose was fibers, from either cotton or wood, through a "heated to 42 C. to 75 C. with the indicated bath of aqueous sodium hydroxide of from 32 to amount of methyl chloride in a closed vessel 38 per cent concentration, at or slightly above until the charge contained only the noted small room temperature, to effect a substantially uniamount of sodium hydroxide. The heating iormsaturation of the sheet with thealkali, and schedule employed in each case was 2 hours at then pressing the sheet, as between suitably 42 C., 2 hours at 52 C., and then at 75 C. to spaced rollers, to reduce the :content of alkali, completion, usually aboutbmore hours. In each and correspondingly'thatoi water, to within the case, the vessel was cooled to stop the reaction recited'limiting ratios to the weight of cellulose. while the mixture was still sligh y afi h Control of this pressing operation is easily vatremaining methyl chloride was accounted for, tained by the standard procedure of .tiimatingthe and the methyl cellulose was analyzed and tested alkali in a weighed sample cut from the alkali for solubility in water and for viscosity of a cellulose sheet, to determine the amount of alstandard aqueous solution. For comparison, kali-therein, and then adjusting the rollerspacsimilar runs were carried out on some .of the ing to allow more alkali to-remaintherein or to same batch of cellulose sheet, but using a 50 expressmore of the alkali, as may be required per cent solution of sodium hydroxide, under one When the proper roller setting has been attained of the heretofore standard procedures. Since for agiven fibrous sheet, further operations need the alkali cellulose from 50 per cent sodium hylittle or no control 'tomaintain the ratios inthe droxide must be kept as cool as possible before stated range. etherification, to minimize degradation of the When an alkali cellulose as just defined is cellulose, all four of the alkali cellulose samples treated in the usual manner with methyl chloride used in these runs were given identical cooling or sulfate at the usual temperatures of etherificatreatment.

TABLE I RunNon. l 2 3 4 sodiumlHydroxidez Concentration, per cent 35 50 50 Temperature of bath, C 70 70 W'tratio,SodiumHydroxide/Gell se 0.93 0.95 0.98 WtJatlmWater/Oellulose 1.67 1.72 0. 05 0.0a Wt. ratio, Methyl Chloride/Cellulose:

Loaded to Reactor 1.10 1.10 1.33 1. 3s ConsumedinReaction 1.06 1.06 1.20 1.21 "Final Sodium Hydroxide in Reactor, Per cen 0. 4 0. l 0 0.1 .Time at Reaction Temperature, Hours 9. 7 0 9. 5 9. 5

Methyl Cellulose:

Viscosity, centipoises, 2 per cent solution in water 17,000 17,500 8,710 0,000 Percent solids, measured on 1 per cent solutioninwater Trace Trace Trace 0.05 Methoxyl, percent 2-7.8 28.1 31.3 30.5 Methoxyl, degreeof substitution 1.68 1.70 1.91 1.86 Methoxyl, equivalent methyl chloride 0.53 0.53 0.60 0. 58 Hence, methyl chloridetoside reactions 0.53 0.53 0.60 0.63 Hence, efficiency, based on charge, per cent 48 i8 44 tion, there is obtained a product which is more 60 From the foregoing table it is observed that, under uniform and more completely soluble than that obtained under similar reaction conditions when usinga lower water or alkali to cellulose ratio in an alkali cellulose prepared either from more dilute or from more concentrated sodium hydroxide solutions. The product has, as well, a much higher viscosity, measured in standard solutionin water than methyl cellulose prepared from the same batch of cellulose :by any known procedure, and no special cooling of the alkali cellulose sheet, during its manufacture and .prior to etherification, is needed to obtain the .said high viscosity products. The product, then, may be used without special treatment commonly reotherwise comparable conditions, the herein claimed ratios of alkali and of water to cellulose, obtained using 35 per cent sodium hydroxide solution, yield a product from these cotton linters of about 17,500 centipoises viscosity while the same cellulose, treated with 50 per cent sodium hydroxide solution, gives a product of from 7,000 to 9,000 centipoises viscosity. Similar runs, made with 35 per cent sodium hydroxide and without any chilling of the alkali cellulose prior to etherification, gave methyl cellulose products whose standard 2 per cent solutions in water had viscosities near 5,000 centipoises. This is over twice the viscosity of .a 2 per cent solution in water of 'q-uired to remove incompletely soluble materials, any commercial methyl cellulose'heretofore available in a water-soluble form. It is noted further tween th tim of its preparation and 'etherifica; that,when' 35 per cent sodium hydroxide is used, tion. 'A comparison of runs-5 and 7 shows that instead of 50 per cent'sodium hydroxide, the it is possible to effect'asaving, according to the charge of methyl chloride per pound of-cellu-lo'se present invention, of 17 per cent in the methyl y e duced 17 per cent, from 1.33 to 1.1 chloridecharged to the reactor, and a further pounds, and the consumption of methyl chloride economy ofaioout 13 per cent in the amount of is reduced 12 percent, from 1.2 to 1.06 pounds, inethyl chloride consumed in the reaction. per pound of cellulose-present. i

Example 3 E m ZT'MethZ/Z cellulose from wood W70 A series, of reactions was carried'out on a num- :In a manner similar to that described in Exber of samples of alkali cellulose all of which had ample 1, a sheet of a.high iscosity type of been Ina-def m the same high viscosity type of high alp -cellulose wood pulp fibers was'converted to "alkalicellulose'by immersion in soluro wood pulpsheet-used in Example 2, and all of which'had been prepared using 35 per cent sodi- 5 um hydroxide solution. The various samples had been pressed to provide a variety of ratios of alkali and'of waterto cellulose. The reaction con ditions were as previously stated in Example 1, except that the alkali cellulose in run number 12 was chilled as soon as it was made and was kept tions of the concentrations ,as-shown in the 1 following Table II. The alkali and water to cellulose: ratios were adjusted by squeezing excess liquor from the alkali cellulose-sheet, and etherification was conducted as before;

114 amine? 0 2L0 0 an interme- TABLE in r, Per Gen cold until charged into the etherifying vessel, While none of the other sampleswer cooled during the corresponding interval before etherificaeidlifii? ydroxide/ Cellulose.

perature, Hours The alkali Water/Cellulose.

but no cooling was used in runs 7, 3

TABLE II Concentration, per cent..... 1 Temperature of bath. C, 1 Weight Ratio, Sodium Hydroxide/Cellulose.

Consumed in reaction: 1 1 1 Final Sodium Hydroxide in Reactor, Per Cent.

cellulose in runs 5 and 6 was chilled before etherification,

and 9.

Sodium ,Hydroxider Weight Ratio, Water/Cellulose. 1

WVeight Ratio, Methyl Chloride/ Cellulose:

Time at Reaction Temperature, Hours Methyl Cellulose:

1,4?0 solution- Viscosity centipoises, 2 per cent solution in Concentration, per cent- Temperature of bath Weight Ratio Sodium H Weight Ratio Loaded to reactor- Consumed inreacti Final Sodium Hydroxide in Time at Reaction Tern Methyl Cellulose:

Viscosity, centipoiscs, 2 per cent solution in Water Per cent solids, measured on 1 per cent solution in Hence, e'ificieney, based on charge, per cen Again it is seen that an alkali cellulose made from per cent sodium hydroxide solution and tion. The'results are'given in Table III.

- Sodium Hydroxide:

Weight Ratio, Methyl Ohlorid water Methoxyl, per cent 1 Methoxyl, degree of substitution Metho Runs 10-12 show that the methyl cellulose prepared from wood cellulose has very poor solubility if the alkali cellulose used as diate has an alkali to cellulose ratio less than 0.9, and a comparison of runs 9 and 11 shows that having an alkaliand a water-to-cellulose ratio within the herein recited preferred range may be etherified under standard conditions to give a methyl cellulose product having from 1.5 to 3 times as high a viscosity as a methyl cellulose prepared under comparable condition from an alkali cellulose derived from 50 per cent sothis difierence in solubility is not due merely to differences in the degree of etherifi-cation. Thus, dium hydroxide. The unexpectedly high visrun 11 gave a product having a methoxyl content cosity product is obtained even when the alkali of 25 4 per cent whose 1 per cent solut1on in water cellulose is uncontrolled as to temperature beshowed that 4 per cent of the methyl cellulose product wasinsoluble, while run 9 .gave. a product having a methoxyl content of 25.9 ,per cent and only0.25 per cent insoluble gels. The product from run 12, in which thealkali cellulose had been chilled, had a viscosity of 1190 centipoises, only slightly higher than the product from runs 10 and 1-1 in which no cooling wasappliedto the alkali cellulose. Runs 7, 8, 9 and 13 all gave methyl cellulose products having viscosities at least double those from runs 10-12, although all products were made from the same cellulose, using the sameconcentration of alkali solution, and employing substantially the same etheriflcation conditions. The high viscosity and improved solubility .can only be "attributed .to'the selected andinarrowrange of ratios of alkali and of water to cellulose in th alkali cellulose subjected 'to etherification.

- The herein-described process, then, makes possible an economy in reagents and provides .a methyl cellulose :from eitherwood-or cotton-fibers which has an improved high solubility in water to yield solutions having from 1.5 to 3 or more times as high a viscosity as solutions of like concentration of methyl cellulose prepared by the heretofore known processes from the same cellulose.

The invention has been illustrated by examples in which the etherifying agent employed was methyl chloride. While this is the least expensive methylating agent available at present, the invention is not limited to the use of this agent. Such other methylating agents as methyl bromide or dimcthyl sulfate may be used with like advantage, whenever the alkali cellulose contains from 0.9 to 1.2 parts of sodium hydroxide and from 1.6 to 225 parts of water per part by weight of cellulose and when these ratios are so interrelated as to represent sodium hydroxide solutions of from 32 to 38 per cent sodium hydroxide concentration, provided that the amount of etherifying agent used is at least equivalent to the amount of sodium hydroxide present and that the etherification reaction is stopped while the reaction mixture isstill slightly alkaline but after most of the alkali has been consumed in the reaction.

In the etherification reactions described in the examples, a uniform temperature schedule was employed consisting of 2 hours at 42 0., 2 hours at52 C., and the balance of the reaction at 75 C. While this is a convenient schedule, and one which can be controlledreadily, it is not deemed critical to the success of the reaction, although etherification temperatures over about C. are found undesirable because of excessive formation of methyl alcohol and methyl ether, and temperaturesof C. or higher are definitely disadvantageous andmust be avoided.

It is recognized that various disclosed processes for making methyl cellulose have been alleged to produce that material in a state which is perfectly solublein cold water. It is not asserted here that the present process makes a product whichis more than perfectly soluble. Ithas been found'that, when 100.milliliters of a 1 per cent solution .of methyl cellulose in water is centri fuged in a Goetztube, .or similarly graduated'apparatuspthe products of the present invention deposit from the merest traceup to a few tenths per cent of a watery gel, while methyl cellulose made by the older methods will deposit correspondingly from'a trace up to several per cent of such gel. In each case, the methyl cellulose from cotton fibers gives a smaller sediment than that from wood pulp.

We claim:

Alkali cellulose containing at least 0.9 and not over 1.2 parts of sodium hydroxide and at least 1.6 and not substantially over 2.25 parts of water, per part of cellulose, by weight, and in which the ratio of alkali to water represents a sodium hydroxide solution of from 32 to 38 per cent.

ALBERT B. SAVAGE. RICHARD W. SWINEHART.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,001,102 Lorand May 14, 1935 2,160,782 Maasberg May 30, .1939 2,285,514 Houghton et al June 9, 1942 FOREIGN PATENTS Number Country Date 435,346 Germany Apr. 29, 1922 OTHER REFERENCES Coward et al; J. Textile Inst. 14, T28, 32 (1923). 

